金属-有机络合聚合物(MOCPs)的研究进展

从配体的角度对中心离子与多齿配体间形成的稳定多孔金属-有机络合聚合物(MOCPs)的发展现状进行了综述。指出该材料自成为研究热点以来,各研究小组在对不同的构件分子进行组合构建新的MOCPs方面富有成效的工作,极大地丰富了络合聚合物的结构数据,但这种材料最引人注目的特性——孔及表面性质的可调控性及其对其各种应用特性,如分子识别、择形催化、择形吸附等所能带来的影响方面的研究还很不够。

水溶性钴络合聚合物的合成与降黏性的评价

以丙烯酸,2-丙烯酰胺-2-甲基丙磺酸,甲基丙烯酰氧乙基三甲基氯化铵,制备出低相对分子质量聚合物,然后再利用此低相对分子质量聚合物与硝酸钴制备出所需的降黏剂。流变性测试表明基浆的降黏率为95%,淡水聚磺高密度模拟浆降黏率为46%,盐水聚磺高密度模拟浆降黏率为45%。抑制性测试表明降黏剂能够抑制地层造浆;黏土表面Zeta电位的变化解释了降黏机理;渗透性实验表明降黏剂能够改善泥饼质量降低钻井液的滤失量;配伍性实验结果显示与其他处理剂配伍性良好。该降黏剂在聚合物泥浆,聚磺高密度泥浆,聚磺低密度泥浆中均有良好的应用效果。

水溶性金属络合聚合物的合成及其润滑性能初探

合成了结构明确的以ＥＤＴＡ锌、铜、钼络合物衍生的水溶性聚合物，考察了该类聚合物用作高水基润滑添加剂的极压、抗磨性能。结果表明，含锌水溶性金属络合聚合物其ＰＢ值为４３１．２Ｎ，长磨磨斑直径Ｄ４０３０为０．５７ｍｍ（添加量为０．５％），优于美国生产的同类产品。

多孔金属-有机络合聚合物结构特征与其吸附行为关系

综述了近来出现的一类有前途的多孔材料——金属-有机络合聚合物(MOCPs)吸附功能的设计策略与合成途径。通过配体结构的选择或修饰可赋予MOCPs特定吸附性的孔环境;或采用适当的设计和合成策略使过渡金属离子和有机配体形成的骨架结构对特定吸附质分子具有特定的选择性。为新型的多孔吸附剂的设计与制备提供了一种新思路。

升深2-17井络合铝聚合物充气钻井液现场试验

为加快徐加固子深层天然气的勘探开发步伐，缩短深层气井的建井周期，在升深2-17井进行了充气钻井试验。介绍了络合铝聚合物充气钻井液技术的现场应用概况及效果以及井漏的发生与处理过程、钻井液起泡的解决措施。在现场试验过程中，络合铝聚合物钻井液性能稳定，具有较强的抑制性和较好的流变性能，流性指数控制在0．7左右，具有良好的携屑和稳定井壁能力，而且粘度较低，基本上控制在33～52s之间，满足了现场充气和脱气的需要；该钻井液抗温可达180℃，润滑性能较好，在钻井过程中无粘卡显示，在深井欠平衡井眼稳定方面取得了较好的效果；在不同的气液比条件下，可以在0．83～1．08g／cm。之间实现对当量密度的调节;与常规钻井工艺相比，充气钻井可以使机械钻速提高30％～50％；在钻进过程中实现了充气和点火同时进行，达到了欠平衡钻井工艺技术的要求，为进一步开展气体钻井打下了良好的基础。

两亲性含镉聚合物金属络合物的制备与表征

采用原子转移自由基聚合(ATRP)方法,制备聚苯乙烯(PS)接枝型引发剂,进而引发甲基丙烯酸丁酯(BMA)与丙烯酸镉(ACd)的共聚合,成功获得PS-g(BMA-co-ACd)接枝共聚物金属络合物。通过傅里叶变换红外吸收光谱、等离子体发射光谱、热重分析对共聚物的组成、结构和性能进行了分析。结果表明,聚合物金属络合物中镉含量测试值与理论值相近,其热稳定性随着镉金属含量的增加稍有降低;通过扫描电镜、透射电镜对聚合物金属络合物在水溶液中自组装形态进行分析,发现其在水溶液中自组装成球形结构的粒子,且稳定性较好;抑菌性测试表明其对大肠杆菌、枯草芽孢杆菌、金黄色葡萄球菌有较好的抑制作用。

含氮聚合物负载钯络合物的合成及其催化加氢性能的研究

合成了一系列含氮聚合物金属络合物,考察了它们对1,5,9-环十二碳三烯选择性催化加氢的活性及选择性。研究了同种聚合物中单原子配体与双原子配体对催化剂活性的影响。对不同金属物种、孔结构、温度及压力对加氢活性及选择性的影响也进行了系统的比较。

日开发出新型聚合物络合乳剂

日本大成精细化学品公司最近开发出一种新型聚合物丙烯酸络合乳剂，其中并存着阴离子和阳离子。产品提供一种高性能的水基树脂，其特性相等于溶剂基型产品，但不会发生凝结现象，公司已把产样提供给用户。

金属络合结构对水基润滑添加剂性能的影响

设计并合成了几种水溶性含有抗磨活性元素P、N、Zn的聚合物添加剂.四球机实验结果表明含Zn络合聚合物的极压.抗磨性能优于美国生产的同类产品Sunsol.通过比较这几种聚合物结构与性能之间的关系发现,Zn元素在添加剂分子结构中的引入及引入方式对添加剂的极压、抗磨性能有显著的影响.以EDTAZn(Ⅱ)

具有手性分离功能的MOCPs的构建

就手性在药物分离中的重要性及手性分离剂的分离机制进行了概述。以此为基础,对一类在手性分离领域有巨大发展潜力的功能材料———金属有机络合聚合物(MOCPs)在分子设计和合成方面的研究现状进行了综述。MOCPs优异的理化性能、孔结构特性和手性分离功能可通过其构建分子的选择和修饰进行设计,其手性结构可通过手性配体与非手性配体进行构建。MOCPs有望在手性分离,特别是在手性药物分离领域形成新的研究和应用的热点。

膜分离技术在重金属废水处理中的应用

综述了电渗析、液膜、纳滤、超低压反渗透、胶束增强超滤和水溶性聚合物络合超滤等膜技术在废水处理中的研究和应用概况,分析了膜技术在处理重金属废水中存在的主要问题,并对膜技术处理重金属废水的发展前景作了展望。

PREPARATION AND PROPERTIES OF GEL POLYMER ELECTROLYTE BASED ON PVDF/ACRYLATE INTERPENETRATING POLYMER NETWORK FOR DYE-SENSITIZED SOLAR CELL

The gel polymer electrolytes（GPEs）based on poly（vinylidence fluoride）（PVDF）/acrylate interpenetrating polymer network（IPN）are prepared.The micro-phase separation type GPEs are characterized by Fourier transform infrared（FTIR）spectroscopy,scanning electron microscope（SEM）,respectively.Moreover,the conductivity and the voltage-current curves of the electrolytes are measured by electrochemical workstation.The higher porosity and electrolyte uptake are observed in the membranes prepared at lower crosslinker concentration.The suitable cross-linking acrylate monomer improves the porosity and the electrochemical behavior of GPE.A dye-sensitized solar cell（DSSC）employing PGE based on PVDF/poly（ethylene glycol dimethacrylate）（PEGDMA）IPN yields an open-circuit voltage of 0.674 V,short-circuit current of 8.476 mA·cm-2and the conversion efficiency of 2.710% under 100 mW·cm-2illumination.

Equilibrium Swelling and Solute Diffusion Characteristics of Poly (Methacrylic Acid co-Poloxamer) Hydrogels

Poly(methacrylic acid co-poloxamer) hydrogel networks were synthesized by free radical solution polymerization and their equilibrium swelling and solute permeation properties were characterized. These gels exhibited pH dependant swelling and solute diffusivity due to the formation or disruption of hydrogen bonded complexation between methacrylic acid (MAA) and etheric (EO). In neutral and basic conditions (above the swelling transition pH), the copolymer swelling was greatly higher than acid condition. In complexed hydrogels, the diffusion coefficients of vitamin B12 (VB12) were in the range of 10-10 to 10-7 cm2s-1; While in uncomplexed hydrogels, the values were about 210-6 cm2s-1. The comonomer composition and synthesis conditions have great effect on the structure, and thereby, swelling and solute diffusion characteristics of the resultant hydrogels. For the copolymers with composition of less than or more than 1:1 MAA/EO molar ratio, the plot of lnD vs 1/H-1 followed two different linear equations of 慺ree volume theory? respectively.

Interpenetrating polymers supported on microporous polypropylene membranes for the transport of chromium ions

Modifying polypropylene membranes with interpenetrating polymer networks(IPNs) through the incorporation of poly(glycidyl methacrylate-N-methyl-D-glucamine)(P(GMA-NMG)) was performed by in situ synthesis via radical polymerization. The surface of the polypropylene membrane was activated by hydrophilic grafted polyelectrolyte, and then, pressure injection was used for the impregnation of the reactive solution in the membrane.Two types of pore-filled membranes were synthesized, chelating interpenetrating homopolymer networks of P(GMA-NMG), and chelating-ion exchange interpenetrating polymer networks(e.g., P(GMA-NMG)/P(AA),P(GMA-NMG)/P(AMPSA), and P(GMA-NMG)/P(Cl VBTA)). After their synthesis, the modified polypropylene membranes were characterized using techniques such as the electrokinetic potential, SEM, FT-IR, and Donnan dialysis to corroborate the chromium ion transport. The P(GMA-NMG) and complex network membranes exhibited a hydrophilic character with a water-uptake capacity between 20% and 35% and a percentage of modification between 4.0% and 7.0% in comparison with the behavior of the unmodified polypropylene membrane.Hexavalent chromium ions were efficiently transported from the food chamber at p H 9.0 when the 65.2%MTA1 P(Cl VBTA) homopolymer IPN membrane and 48.5% MTAG P(GMA-NMG)/P(Cl VBTA) IPN membrane were used. Similarly, hexavalent chromium ions were removed from the food chamber at pH 3.0 when MTAG(63.30%) and MTA1(35.68%) were used in 1 mol·L^(-1)Na Cl solution as the extraction reagent.

Preparation and Aqueous Recognition of Metal Complex Imprinted Polymer Using N-vinyl-2-pyrrolidone as Functional Monomer

Using nickel（II） acetate.-2,2＇-dipyridyl complex as template and N-vinyl-2-pyrrolidone （NVP） as coordinate functional monomer,.a new kind of metal-compiexing template molecularly impnnted polymer （MIP） was prepared..The results of equilibri.um binding experiments in. aqueous solution showed that the MIP had higher＇binding capacity for nickel（ II ）-2,2＇-dipyridyl than the non-imprinted polymer with the same chemical composition. Theinfluences of metal ions and pHof solution on the recognition performance of MIP were investigated. The bindingcharacteristics of MIP were evaluated by the Scatchard analysis with one-site and two-site binding equations, respectively. The results on substrate selectivity of imprinted polymer revealed that MIP had better binding affinityfor template among thetested compounds.

Study on Catalytic Properties of Cyclopentadienyl Bisphenoxyl Titanium Chloride for Ethylene Polymerization via Molecular Simulation

Three mono-cyclopentadienyl metal complexes, [C_6H_4O_2]CpTiCl (Ⅰ),[C_(12)H_8O_2]CpTiCl (Ⅱ), and [C_(20)H_(12)O_2] CpTiCl (Ⅲ), were prepared via the reactions ofcyclopentadienyl titanium trichloride with catechol, 2,2i-bisphenol, and 2,2'-bisnaphthol,respectively. In the presence of a moderate amount of methylaluminoxane (MAO), the complexesexhibited catalytic activities for ethylene polymerization. Complex Ⅰ showed the highest activityat Al/Ti molar ratio of 500 at the temperature of 30℃. With increasing of polymerizationtemperature, catalytic activities and molecular weight of the obtained polyethylene tended todecrease, and molecular weight distribution of polyethylene became narrower. With the molecularsimulation method, the charges on titanium atoms of complexes Ⅰ, Ⅱ, and Ⅲ, and the bond anglesformed by Ti and bisphenoxy ligands were calculated. It was concluded that the smaller the netcharge on Ti and the smaller the angle of O1―Ti―O2, the higher the activity of the complex.

Preparation and adsorption behaviors of Cu(Ⅱ) ion-imprinted polymers

Imprinted polymers were prepared for selective removal of Cu（Ⅱ） ions from metal solutions. Three ion-imprinted polymers were synthesized with methacrylic acid （MAA）, acrylamide （AA） and N,N＇-methylenebisacrylamide （MBAA） respectively as the functional monomers, ethleneglycoldimethacrylate （EGDMA） as the cross-linking agent, 2,2＇- azobisisobutyronitrile （AIBN） as the initiator and Cu （Ⅱ） ion as the imprint ion. The template Cu （Ⅱ） ion was removed from the polymer by leaching with a liquid of a 1：1 volumetric ratio of HCl to ethylenediaminetetraacetic acid （EDTA）. The capacity and selectivity of Cu（Ⅱ） ion adsorption were investigated with the three imprinted polymers and their non-imprinted counterparts. The polymers have a maximum adsorption capacity at pH 7.0. The isotherm of their batch adsorption of Cu（Ⅱ） ions shows a Langmuir adsorption pattern. Imprinted polymers all have a much higher capacity and higher selectivity of Cu（Ⅱ） adsorption than nonimprinted ones. MAA polymer benefits the most from imprinting. Imprinted MAA polymer has the highest selectivity when used to rebind Cu （Ⅱ） ion from an aqueous solution in the presence of other metal ions. Ion imprinting can be a promising technique of preparing selective adsorbents to separate and preconcentrate metal in a medium of multiple competitive metal ions through solid phase extraction （SPE）.

纤维素氧膦-钯络合物催化合成二元酮化物的研究

本文首次采用纤维素氧膦 -钯络合物为催化剂 ,以丙酮为溶剂 ,有机锡试剂与二元酰氯偶联合成二元酮化物。该反应具有催化活性高、选择性强、反应条件温和、催化剂可以重复使用、在空气中稳定等特点 ,是由易得二元酸合成二元酮的新方法。

STUDY ON SYNTHESIS AND RELAXIVITY OF PARAMAGNETIC POLYESTER METAL COMPLEXES FOR MRI

Fifteen new polyester ligands were prepared by copolymerndion Of EDTA(ethylenediaminetetraacetic acid ) dianhydride or DTPA (dikthylenetriaminepenlaacetic acid) dianhydrtde and dihydric alcohol or dihydric phenol. Theirparanzagnetic metal complexes were also synthesized. All polyester ligands andmetal complexes were characterized by IHNMR, IR spectra and elemental analyses. Preliminary study showed that the polyester .metal complexes had higher relaxation effectiveness as compared to corresponding small molecular metal complexes.